The 5th China-Japan
Young Chemists Forum

Molecular Activation
Directed toward
Straightforward
Organic Synthesis
The Chemical Society of JapanThe 95th Annual Meeting
March 27th, 2015
Venue Funabashi Campus, Nihon University,
Chiba, Japan
Date

Welcome Address
Welcome to the 5th China-Japan Young Chemists Forum, heldat the same venue as the 95th CSJ Annual Meeting, Funabashi Campus,
College of Science and Technology, Nihon University, Chiba, Japan on
March 27th, 2015, under the co-sponsorship of the Chinese Chemical
Society (CCS) and the Chemical Society of Japan (CSJ).
The CSJ has a history of 137 years, with a current membershipof about 30,000, and is one of the most influential learned societies in Japan, covering mostareas of pure and applied chemistry both in academia and industry.
Our prime mission is to contribute to social development through advancing science,developing technology, promoting industry, diffusion of knowledge relating to chemistry, anddeveloping human resources. To pursue this mission, the CSJ holds various conferences, suchas "the CSJ Annual Meeting" with 8,500 participants every spring, and "CSJ Chemistry Festa"
every autumn.
This series of bilateral meetings originates from the first one in 2010 held in Xiamen
University, followed by the second in 2012 at Sichuan University and the third in 2013 at
Ritsumeikan University during the 93rd CSJ Annual Meeting. The fourth Forum was held in2014 at Peking University during the 29th CCS Annual Meeting“A Molecular Activation Directed toward Straightforward Organic Synthesis”, thetopic of the 2015 China-Japan Forum is a highly advanced interdisciplinary field that covers
from organotransition metal chemistry to organic synthesis, featuring novel metal complexes
that enable activation of unreactive C–H and C–C bonds, catalytic CO2 fixation, novel radical
reactions, catalytic C–H and C–O functionalizations and their applications to total synthesisof natural products. Ten distinguished scientists in the area of advanced measurements areinvited to present their research results and to exchange information and ideas.
I would like to thank co-Chairs Prof. NAKAO, Yoshiaki, Kyoto University and Prof.
SHI, Zhang-Jie, Peking University, for their great efforts to make this forum possible. It is myhope that this joint event will contribute to the rapid development of this field toward useful
applications and I also have great expectations that all of the attendants will strengthen theirfriendships and find new colleagues throughout the forum and the CSJ Annual Meeting for
further collaboration.

Mr. Nobuyuki Kawashima
Executive Director / Secretary General
The Chemical Society of Japan
kawashima@chemistry.or.jp

The 5th China‐Japan Young Chemists Forum―Molecular Activation Directed toward Straightforward Organic Synthesis―
The Chemical Society of Japan The 95th Annual Meeting

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Date
March 27th (Fri), 2015 10:00‐17:10
Venue Room 1424 (S6) 2nd Floor 14th Bldg.,
Funabashi Campus, Nihon University, Chiba, Japan
Hosted by The Chemical Society of Japan (CSJ)
Co‐hosted by The Chinese Chemical Society (CCS)■10:00Opening Remarks

Zhang‐Jie SHIPeking University…1■10:10One or Two Electron Redox, Radical Oxidative Coupling
and Mechanism Revealed by Operando XAS, Raman, EPR,
and IRC‐H and C‐C Bond Cleavage by Using Group 9 Metal
Complexes Possessing a Boron‐Based Pincer Ligand

Aiwen LEI
Wuhan University…2

Makoto YAMASHITA
Chuo University…4

Qian ZHANG…6■10:40■11:10■11:40■12:10C‐N Bonds Construction Based on Nitrogen‐Centered
Radicals
Carboxylation of Unsaturated Hydrocarbons with CO2
Catalyzed by Palladium Complexes Bearing a Group 14
Element‐based Pincer Type Ligand
Highly Efficient Methodologies via Aerobic Oxygenation

Northeast Normal University

Jun TAKAYA…8Tokyo Institute of Technology

Ning JIAO, et al.
Peking University…10

Lunch Break■12:40■14:30

Directed C‐H Bond Activation Using Iron Catalysis

Laurean ILIES, et al.
The University of Tokyo

…12■15:00

Phosphine‐Participated C‐H Transformation

Shang‐Dong YANG
Lanzhou University…14■15:30A C‐H Arylation/Ring Transformation Approach:
Synthesis of Polyarylated Arenes and Natural Products

Junichiro YAMAGUCHI
Nagoya University…16■16:00Act like Molecule Transformers－
Rapid Creation of Molecular Complexity throughStrategic Bond Disconnections
Cross‐Coupling Reactions via the Activation of Inert
Carbon‐Oxygen Bonds

Guangxin LIANG
Nankai University…18

Mamoru TOBISU
Osaka University…20

Closing Remarks

Yoshiaki NAKAO
Kyoto University…22■16:30■17:00ｃ
5th CCS-CSJ,
Young Chemists Forum

Zhang-Jie SHI
College of Chemistry and Molecular Engineering
Peking University Beijing 100871 China
E-mail: zshi@pku.edu.cn
Homepage: http://www.chem.pku.edu.cn/zshi/
Educational Background1992-1996
East China Normal University, B.Sc.
1996-2001
Shanghai Institute of Organic Chemistry, CAS,
(Supervised by Professor Shengming Ma), Ph.D

Academic Career
2001-2002 Harvard University (Mentor: Professor Gregory L. Verdine), Fellow
2002-2004 The University of Chicago (Mentor: Professor Chuan He), Associate
2004-2008 Peking University, Associate Professor
2008-present Peking University, Professor
2012-present Peking University, Changjiang Professor



Research Interests
Zhangjie Shi and his team are aiming at developing efficient and economic synthetic
methodologies as well as understanding the intrinsic properties of the inert bonds to meet therequirement of green and sustainable development. His current work is focused on directtransformations of “inert” chemical bonds, including C-O, C-H and C-Cs.

AwardsChief Scientist for “973" Project from MOST (2014), National Excellent Contributor in Science andTechnology (2014), HLHL Innovative Award of Science and Technology (2014), Mr. and Mrs. Sun
Chan Memorial Award (2014), Highly Cited Researcher (2014), Mao Yisheng Young InvestigatorAward of Science of Technology of Beijing City (2013), The Second Rank Award of National
Natural Sciences (2013), OMCOS Award (2013), Wuxi Apptec Excellence Chemistry Award forLife Sciences (2012), Lilly Excellence Chemistry Award (2012), ACP Lectureship Award (2012,
Japan and Singapore), Tetrahedron Young Investigator Award (2011), CCS-RSC Excellent Young
Chemist Award (2011), SFB Guest Professorship (University of Munster, Germany, 2010), Adjunct
Professor (Beijing University of Science and Technology, 2010), Scopus Young Star of Sciences(2010), Distinguished Young Investigator Foundation (NSFC, 2009), New Star on Creative
Research of Beijing City (2009), P&G Excellent Teaching Award (2008) CAPA Distinguished
Professor Award (2008), The First Rank Fok Ying Tung Education Foundation Award (2008), CCSJohn Wiley Excellent Chemistry Award (2008), The Second Rank Award of National Natural
Sciences (2007), Distinguished Young Chemist Award of Chinese Chemical Society (2007),Synlett/Synthesis Journal Award (2006), The First Rank Award of Science and Technology ofShanghai City (2005)



Recent Publications
118 (cited by others: more than 7500, H index: 46)



EditedHomogeneous Catalysis in C-X Activation (Editor, 2014), C-H Activation (Co-Editor), and other 6
chapters in different books.

1ｃ
5th CCS-CSJ,
Young Chemists Forum

2

Aiwen LEI
Professor of Chemistry
College of Chemistry and Molecular Sciences, Wuhan University
Address: Luojiashan, Wuchang, Wuhan, Hubei, China
Tel: (+86)-27-68754672
E-mail: aiwenlei@whu.edu.cn


Educational Background1995 B.Sc., Huaibei Normal University
2000 Ph.D., Shanghai Institute of Organic Chemistry (supervisor: Prof. Xiyan Lu)

Professional Career
2000-2003 Postdoctoral Fellow, Pennsylvania State University
2003-2005 Research Associate, Stanford University
2005- now Professor, Wuhan University



Research Interests
1) Developing highly selective and efficient transition-metal-catalyzed C-C, and Cheteroatom bond formation in syntheses, e.g. oxidative coupling reactions, C-H bondfunctionalization
2) Mechanistic studies including kinetic and active intermediate studies

Awards2008 Chinese Chemistry Society－John Wiley Young Chemist Award
2009 CAPA Distinguished Faculty Award
2010 National Science Fund for Distinguished Young Scholars, China
2011 Eli Lilly Scientific Excellence Award in Chemistry2012 First-Class Natural Science Award of Hubei Province2013 Asian Rising Stars (15th ACC Meeting)2014 Chinese Chemistry Society－Royal Society of Chemistry Young Chemist
Award



Recent Publications
1. "From Anilines to Isatins: Palladium-Catalyzed Oxidative C−H Double Carbonylation ", Wu Li,
Zhengli Duan, Xueye Zhang, Heng Zhang, Mengfan Wang, Ru Jiang, Hongyao Zeng, Chao Liu
and Aiwen Lei. Angew. Chem. Int. Ed. 2015, DOI: 10.1002/anie.201410321.
2. "Chloroacetate-Promoted Selective Oxidation of Heterobenzylic Methylenes under Copper
Catalysis ", Jianming Liu, Xin Zhang, Hong Yi, Chao Liu, Ren Liu, Heng Zhang, Kelei Zhuo, andAiwen Lei. Angew. Chem. Int. Ed. 2015, DOI: 10.1002/anie.201409580.
3. "Direct Observation of Reduction of Cu(II) to Cu(I) by Terminal Alkynes", Guanghui Zhang, Hong
Yi, Guoting Zhang, Yi Deng, Ruopeng Bai, Heng Zhang, Jeffrey T. Miller, A. Jeremy Kropf,
Emilio E. Bunel, and Aiwen Lei. J. Am. Chem. Soc. 2014, 136, 924.
4. "Visible Light Mediated Decarboxylation / Oxidative Amidation of α-Keto Acids with Amines
under Mild Conditions Using O2", Jie Liu, Qiang Liu, Hong Yi, Chu Qin, Ruopeng Bai, Xiaotian
Qi, Yu Lan, and Aiwen Lei. Angew Chem Int Ed 2014, 53, 502.

Molecular Activation Directed toward Straightforward Organic Synthesis

One or Two Electron Redox, Radical
Oxidative Coupling and Mechanism Revealed
by Operando XAS, Raman, EPR, and IR
Aiwen LEI
College of Chemistry and Molecular Sciences, Wuhan University,
Hubei 430072, P. R. China
Our research focuses on the oxidative coupling to develop a novel and efficient bondformation method between two nucleophiles. We have successfully developed three
generations of oxidative coupling. In addition, in-depth understanding toward thereactions is the other focus. Recently, a new series of oxidative coupling reactions havebeen developed. New insights into the reaction mechanism have also been revealed byoperando X-ray absorption, Raman, electron paramagnetic resonance, and nuclear

magnetic resonance spectroscopy.

References(a) Liu, C.; Zhang, H.; Shi, W.; Lei, A. W., Chem. Rev. 2011, 111 (3), 1780-1824; (b) Liu, Q.;
Zhang, H.; Lei, A. W., Angew. Chem. Int. Ed. 2011, 50 (46), 10788-10799; (c) He, C.; Ke, J.; Xu, H.;
Lei, A. W., Angew. Chem. Int. Ed. 2013, 52 (5), 1527-1530; (d) He, C.; Zhang, G. H.; Ke, J.; Zhang,H.; Miller, J. T.; Kropf, A. J.; Lei, A. W., J. Am. Chem. Soc. 2013, 135 (1), 488-493.

3

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4

5th CCS-CSJ, Young Chemists Forum

Makoto YAMASHITA
Associate Professor of Chemistry
Department of Applied Chemistry, Faculty of Science and Technology,
Chuo University
Address: 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan
Tel & Fax: (+81)-3-3817-1902
E-mail: makoto@oec.chem.chuo-u.ac.jp
URL: http://www.chem.chuo-u.ac.jp/~element/index-e.html
Educational Background1997 B.Sc., Hiroshima University (supervisor: Prof. Kin-ya Akiba)
1999 M.Sc., Graduate School of Science, Hiroshima University (supervisor: Prof. Kin-ya
Akiba)
2002 Doctor of Science, Graduate School of Science, Hiroshima University (supervisors:
Profs. Kin-ya Akiba, Yohsuke Yamamoto)Professional Career
2001 JSPS research fellow (DC2,PD)
2002 postdoctoral fellow, Yale University (Prof. John F. Hartwig)
2003 postdoctoral fellow, The University of Tokyo (Prof. Takayuki Kawashima)
2004 Research Associate, The University of Tokyo (w. Prof. Kyoko Nozaki)
2007 Assistant Professor, The University of Tokyo
2008 Senior Lecturer, The University of Tokyo
2011 Associate professor (Principal Investigator), Chuo University



Research Interests
1) Organometallic chemistry for homogeneous catalyst
2) Main group chemistry for new species, structure, and properties
3) Chemistry of coal tars for organic devices in futureAwards
2005 Inoue Research Award for Young Scientist
2009 Chemical Society of Japan Award for Young Chemists
2009 The Young Scientists' Prize from the Minister of Education, Culture, Sports, Scienceand Technology
2010 Banyu Chemist Award
2015 Thieme Chemistry Journal Award

Recent Publications
1. "Synthesis, Structure, and Bonding Properties of Ruthenium Complexes Possessing a
Boron-Based PBP Pincer Ligand and Their Application for Catalytic Hydrogenation"
Miyada, T.; Huang Kwan, E.; Yamashita, M., Organometallics 2014, 33, 6760.
2. "Assessing the Brønsted Basicity of Diaminoboryl Anions: Reactivity toward Methylated
Benzenes and Dihydrogen" Dettenrieder, N.; Aramaki, Y.; Wolf, B. M.;
Maichle-Mössmer, C.; Zhao, X.; Yamashita, M.; Nozaki, K.; Anwander, R., Angew.
Chem. Int. Ed. 2014, 53, 6259.
3. "Facile scission of isonitrile carbon–nitrogen triple bond using a diborane(4) reagent"
Asakawa, H.; Lee, K.-H.; Lin, Z.; Yamashita, M., Nat. Commun. 2014, 5, 4245.

Molecular Activation Directed toward Straightforward Organic Synthesis

5

C-H and C-C Bond Cleavage
by Using Group 9 Metal Complexes
Possessing a Boron-Based Pincer Ligand
Makoto YAMASHITA
Department of Applied Chemistry, Faculty of Science and Technology, Chuo University
1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan"Pincer ligand" is a class of tridentate ligand coordinating to metal atoms in a meridional
fashion. Recently, activation reactions of inert bonds and small molecules using pincer
complexes have been widely explored. On the other hand, transition metal boryl complexes
have been interested in their catalytic performance and very strong donor ability of boryl
ligand.1 However, it is difficult to utilize the boryl complex for catalytic reaction other thanborylation due to the high reactivity of anionic boryl ligand. Recently, we reported synthesisof a novel boron-containing tridentate PBP-pincer ligand precursor and its complexation withtransition metals.2 Herein, we report reactivity PBP-pincer Rh complexes toward O-H bond of
phenol and aliphatic alcohols and C-C bond of benzocyclobutenone (Scheme 1).3 The similar
PBP-pincer Ir complexes possessing a structurally modified pincer ligand were also found to
catalyze the transfer dehydrogenation of cyclooctane in the presence of hydrogen acceptor(Scheme 2).4 Catalytic activity of these complexes were altered by the structure of the ligand.
In the presentation, details about chemistry of newly obtained PBP-pincer complexes will bereported.

References
1. Irvine, G. J.; Lesley, M. J. G.; Marder, T. B.; Norman, N. C.; Rice, C. R.; Robins, E. G.; Roper, W.
R.; Whittell, G. R.; Wright, L. J., Chem. Rev. 1998, 98, 2685-2722.
2. (a) Segawa, Y.; Yamashita, M.; Nozaki, K., J. Am. Chem. Soc. 2009, 131, 9201. (b) Segawa, Y.;
Yamashita, M.; Nozaki, K., Organometallics 2009, 28, 6234. (c) Miyada, T.; Yamashita, M.,
Organometallics 2013, 32, 5281-5284. (d) Ogawa, H.; Yamashita, M., Dalton Trans. 2013, 42,625-629. (e) Miyada, T.; Huang Kwan, E.; Yamashita, M., Organometallics 2014, 33, 6760-6770. (f)Ogawa, H.; Yamashita, M., Chem. Lett. 2014, 43, 664-666.
3. (a) Hasegawa, M.; Segawa, Y.; Yamashita, M.; Nozaki, K., Angew. Chem. Int. Ed. 2012, 51, 6956.
(b) Y. Masuda, M. Hasegawa, M. Yamashita, K. Nozaki, N. Ishida, M. Murakami, J. Am. Chem. Soc.
2013, 135, 7142.
4. Kawai, J. Y.; Tanoue, K.; Yamashita, M. unpublished results.

6

5th CCS-CSJ, Young Chemists Forum

Qian ZHANG
Professor of Department of Chemistry, Northeast Normal
University
Address: Renmin Street, 5268 Changchun, China,130024
Tel & Fax: (+86)-431-85099759
E-mail: zhangq651@nenu.edu.cn


Educational Background1993 B.Sc., Northeast Normal University,
1996 M.Sc., Northeast Normal University, (supervisor: Prof. Qun Liu)
2003 Changchun Institute of Applied Chemistry, CAS (supervisor: Prof. Lixiang Wang)

Professional Career2004 The University of Sydney, Australia, 2004 (Visiting Scholar)
2004 Assistant professor, Northeast Normal University
2008 Professor, Northeast Normal University



Research Interests
1) the area for the construction of C–N bonds2) the development of new radical amination reagentsAwards2014

Thieme Chemistry Journals Award

Recent Publications
1. Palladium-Catalyzed C–H Aminations of Anilides with N-Fluorobenzenesulfonimide, K.
Sun, Y. Li, T. Xiong, J. Zhang, Q. Zhang,* J. Am. Chem. Soc., 2011, 133, 1694-1697.
2. Copper-Catalyzed Dehydrogenative Cross-Coupling Reactions of N-p-Tolylamides throughSuccessive C–H Activation: Synthesis of 4H-3,1-Benzoxazines, T. Xiong, Y. Li, X. Bi,* Y.
Lv, Q. Zhang,* Angew. Chem., Int. Ed., 2011, 50, 7140-7143.
3. Highly
Regioselective
Copper-Catalyzed
Benzylic
C–H
Amination
by
N-Fluorobenzenesulfonimide, Z. Ni, Q. Zhang,* T. Xiong, Y. Zheng, Y. Li, H. Zhang, J.
Zhang,* and Q. Liu,* Angew. Chem., Int. Ed., 2012, 51, 1244-1247.
4. Copper-Catalyzed Intermolecular Aminocyanation and Diamination of Alkenes, H. Zhang,
W. Pu, T. Xiong,* Y. Li,* X. Zhou, K. Sun, Q. Liu, and Q. Zhang,* Angew. Chem., Int. Ed.,2013, 52, 2529-2533.
5. Regioselective Radical Aminofluorination of Styrenes, H. Zhang, Y. Song, J. Zhao, J.
Zhang,* and Q. Zhang,* Angew. Chem., Int. Ed., 2014, 53, 11079-11083.

Molecular Activation Directed toward Straightforward Organic Synthesis

C–N Bonds Construction Based on
Nitrogen-Centered Radicals
Qian ZHANG
Department of Chemistry, Northeast Normal University, Changchun 130024,
P. R. China

The construction of C–N bond is of great importance because of the interesting anddiverse biological activities of nitrogen-containing compounds. Nitrogen-centeredradicals, highly reactive and short-lived species, have been efficiently employed inamination reaction. However, compared with the well established nucleophilic andelectrophilic amination reaction, the construction of C-N bonds based on
nitrogen-centered radicals have not received sufficient attention, which can be partly
attributed to harsh conditions for the generation of nitrogen-centered radicals and theirleading propensity for hydrogen abstraction or engaging in other degradation pathway.
Recently, radical fluorine atom transfer reaction of N-Fluorobenzenesulfonimide(NFSI) was realized, which suggested that NFSI might become a radical amiantion
reagent. Through the well combination of copper catalysts and NFSI, acted as copper
stablized nitrogen-centered radical, for the first time, we realized benzylic C(sp3)–H
direct amination reactions, highly regio-selective aminative difunctionalization reactionsof alkenes and aminative multiple-functionalization of alkynes (Figure 1).

F N

SO2Ph new radical

aminating
SO2Ph reagent
N-Fluorobenzenesulfonimide(NFSI)

N

SO2Ph
SO2Ph

R1

R2

N(SO2Ph)2
from benzylic C(sp3)-H
Angew. Chem. Int. Ed.,2012, 51, 1244.

CN
2

1

R

R

N(SO2Ph)2

NHCOR
R2
R1
N(SO2Ph)2

F
R1

O

R2
N(SO2Ph)2

from alkenes
Angew. Chem. Int. Ed., 2013, 52, 2529; 2014, 53, 11079.

R1

NHSO2PhPh R2from alkynes

Figure 1. Amination Reactions with N-Fluorobenzenesulfonimide as Nitrogen-centered
Racidal.

7

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5th CCS-CSJ, Young Chemists Forum

Jun TAKAYAAssociate Professor
Department of Chemistry, Tokyo Institute of Technology
Address: 2-12-1-E1-2, O-okayama, Meguro-ku, Tokyo,152-8551, Japan
Tel & Fax: (+81)-3-5734-2766
E-mail: takayajun@chem.titech.ac.jp
Educational Background1999
B.Sc., Gakushuin University (supervisor: Prof. Takahiko Akiyama)
2001
M.Sc., Graduate School of Science, Gakushuin University (supervisor: Prof.
Takahiko Akiyama)
2004
Doctor of Schience, Graduate School of Science and Engineering, Tokyo Instituteof Technology (supervisor: Prof. Nobuharu Iwasawa)Professional Career
2004
JSPS postdoctoral fellow, Yale University
2005
Assistant professor, Tokyo Institute of Technology
2014
Associate professor, Tokyo Institute of Technology

Research Interests
1) Design, synthesis, and utilization of functional transition metal complexes2) Development of new synthetic reactions

Awards
2013
2014
2014
2014



Incentive Award in Synthetic Organic Chemistry, Japan
Banyu Chemist Award
Thieme Chemistry Journal Award 2015
Lectureship Award MBLA 2014

Recent Publications
1. "Direct Carboxylation of Simple Arenes with CO2 through a Rhodium-Catalyzed C–H Bond
Activation" T. Suga, H. Mizuno, J. Takaya, N. Iwasawa, Chem. Commun, 2014, 50, 14360.
2. "Silyl Ligand-Mediated Reversible β-Hydrogen Elimination and Hydrometallation at
Palladium" J. Takaya, N. Iwasawa, Chem. Eur. J., 2014, 20, 11812.
3. "Mechanistic Studies on the Stereoisomerization between Two Stereoisomeric, Isolable
Five-Coordinate Borylpalladium(II) Complexes Bearing a Phenylene-Bridged PSiP-Pincer
Type Ligand" J. Takaya, N. Kirai, N. Iwasawa, Organometallics, 2014, 33, 1499.
4. "PSiP-Pincer Type Palladium-Catalyzed Dehydrogenative Borylation of Alkenes and1,3-Dienes" N. Kirai, S. Iguchi, T. Ito, J. Takaya, N. Iwasawa, Bull. Chem. Soc. Jpn., 2013,
86, 784.
5. "Palladium(II)-Catalyzed Direct Carboxylation of Alkenyl C–H Bonds with CO2" K. Sasano, J.
Takaya, N. Iwasawa, J. Am. Chem. Soc., 2013, 135, 10954.
6. "Two Reversible sigma-Bond Metathesis Pathways for Boron-Palladium Bond Formation:
Selective Synthesis of Isomeric Five-Coordinate Borylpalladium Complexes" N. Kirai, J.
Takaya, N. Iwasawa, J. Am. Chem. Soc., 2013, 135, 2493.

9

Molecular Activation Directed toward Straightforward Organic Synthesis

Carboxylation of Unsaturated Hydrocarbons with CO2
Catalyzed by Palladium Complexes Bearing a Group
14 Element-based Pincer Type Ligand
Jun TAKAYA
Department of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo,152-8551, Japan
We have been developing new synthetic reactions utilizing palladium complexes
bearing a PSiP–pincer type ligand as a catalyst. Salient features of the PSiP–palladium
complex are as follows; 1) Strong trans influence of the silicon atom enhances
reactivity of its trans substituent. 2) The strained square planar structure of the
PSiP-linkage facilitates structural change to trigonal bipyramidal geometry, allowing
unique fluxional behaviors of the silicon atom via an η2–(Si–H)Pd(0) intermediate.
Consequently, we have developed hydrocarboxylation reaction of unsaturatedhydrocarbons with CO2 and selective dehydrogenative borylation of alkenes and dienes
with diboron by utilizing characteristics of the PSiP–palladium complexes.
Furthermore, new reaction mechanisms for bond activation and formation with
η2–(Si–H)Pd(0) intermediate through fluxional behavior of the silicon ligand wererevealed, demonstrating promising utility of the PSiP–pincer ligand in organometallic
and synthetic chemistry. In this presentation, we describe recent progress in the
PEP-palladium-catalyzed CO2-fixation reaction (E=group 14 element) and some newmechanistic insights into η2–(Si–H)Pd(0)-mediated molecular transformations.

X
Ph 2P

Pd

PPh 2

E
R
unsaturatedhydrocarbons

CO 2+
reductant

R 2 COOH

R 2 COOH

R1

R1
H

H
R3

Figure 1. New CO2-fixation reactions catalyzed by PEP-palladium complexes (E=Si, Ge).

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5th CCS-CSJ, Young Chemists Forum

Ning JIAO
Professor of Chemistry
State Key Laboratory of Natural and Biomimetic Drugs,
School of Pharmaceutical Sciences, Peking University,
100191 Beijing, China
Tel & Fax: +86-10-8280-5297
E-mail: jiaoning@pku.edu.cn
Home Page: http://sklnbd.bjmu.edu.cn/nj

Educational Background
1999
2004
2006



Professional Career
2007
2010



B.Sc., Shandong University, 1995-1999
Ph.D., Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (withProf. Shengming Ma), 1999-2004
Postdoctoral, Max Planck Institute für Kohlenforschung (MPI), Germany, Alexander von
Humboldt Fellowship (with Prof. Manfred T. Reetz ), 2004-2006

Associate professor, Peking University
Professor, Peking University

Research Interests
Jiao's research interests are focused on: 1) To develop green and efficient synthetic
methodologies through Single Electron Transfer (SET) process; 2) Aerobic oxidation,
Oxygenation and Nitrogenation reactions; 3) The activation of inert chemical bonds catalyzed by
the first-row transition metal catalysts.

Awards
2013
2013
2013
2012
2010
2010
2008



National Science Fund for Distinguished Young Scholars
The Chinese Homogenous Catalysis Young Chemist Award
Thieme Journal Award
National Youth Top-notch Talents
Young Chemist Award of the Chinese Chemical Society
CAPA Distinguished Faculty Award
New Century Excellent Talents in University Award from Chinese Ministry of Education

Recent Publications
1.
2.
3.
4.
5.

Yu-Feng Liang and Ning Jiao*, Transition-Metal Free Highly Efficient C-H Hydroxylationof Carbonyls with Molecular Oxygen Under Mild Conditions, Angew. Chem. Int. Ed. 2014,
53, 548.
Teng Wang and Ning Jiao*, TEMPO-catalyzed Aerobic Oxygenation and Nitrogenation of
Olefins via C=C Double Bond Cleavage, J. Am. Chem. Soc. 2013, 135, 11692.
Shengtao Ding, and Ning Jiao*, The Direct Transformation of DMF(N,N-Dimethylformamide) to -CN: Pd-catalyzed Cyanation of Heteroarenes via C-H
Functionalization. J. Am. Chem. Soc. 2011, 133 (32), 12374-12377.
Chun Zhang, and Ning Jiao*, Dioxygen Activation at Ambient Conditions: Cu-catalyzed
Oxidative Amidation-Diketonization of Terminal Alkynes. J. Am. Chem. Soc. 2010, 132,
28-29.
Teng Wang, and Ning Jiao*, Direct Approaches to Nitriles via Highly Efficient
Nitrogenation Strategy through C–H or C–C Bond Cleavage, Acc. Chem. Res. 2014, 47,
1137.

Molecular Activation Directed toward Straightforward Organic Synthesis

Highly Efficient Methodologies via
Aerobic Oxygenation
Ning JIAO,* Chun ZHANG, Yijin SU, Riyuan LIN, Teng WANG, Yuepeng YAN,
Xiang SUN, Yufeng LIANG, and Zejun XU
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical
Sciences, Peking University, Beijing 100191, P. R. China
On the behalf of green and sustainable chemistry, molecular oxygen has been
considered as an ideal oxidant and offers attractive academic and industrial
prospects.1 Recently, we developed some direct dehydrogenative transformations
using O2 as the oxidant including the Direct-Dehydrogenative Anulation (DDA)
reactions for the synthesis of heterocyclics. Using inexpensive iron, copper ororganocatalyst as the catalysts, some approaches to the amides, ketones, diynes,
ynamides and azo compounds could be highly efficiently synthesized using O2 asoxidant and reactant. In this seminar, I would like to introduce some cases on the
aerobic oxygenations via dioxygen activation through radical pathway.

O2+

Aerobic Oxidative
Functionalization

C

FG

C X
Oxygenation
X = H or C

C O

Keywords: Aerobic Oxidation, Oxygenation, Molecular Oxygen
References:
1 (a) Punniyamurthy, T.; Velusamy, S.; Iqbal, J. Chem. Rev. 2005, 105, 2329. (b) Stahl, S. S. Angew.
Chem., Int. Ed. 2004, 43, 3400. (c) Gligorich, K. M.; Sigman, M. S. Angew. Chem. Int. Ed. 2006,
45, 6612. (d) Wu, W.; Jiang, H. Acc. Chem. Res., 2012, 45, 1736. (e) Shi, Z.; Zhang, C.; Tang, C.;
Jiao, N. Chem. Soc. Rev. 2012, 41, 3381. (f) Zhang, C.; Tang, C.; Jiao, N. Chem. Soc. Rev. 2012, 41,3464.
** We thank the National Science Foundation of China (No. 21172006) and National Basic
Research Program of China (973 Program) (Grant No. 2009CB825300) for financial support.

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5th CCS-CSJ, Young Chemists Forum

Laurean ILIESAssociate Professor of Chemistry
Department of Chemistry, School of Science, The University ofTokyo
Address: 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Tel & Fax: +(03)-5841-4368
E-mail: laur@chem.s.u-tokyo.ac.jp
Educational Background2004 B.Sc., The University of Tokyo (supervisor: Prof. Eiichi Nakamura)2006 M.Sc., Graduate School of Science, The University of Tokyo (supervisor:
Prof. Eiichi Nakamura)2009 Doctor of Science, Graduate School of Science, The University of Tokyo(supervisor: Prof. Eiichi Nakamura)

Professional Career2009 The University of Tokyo (PD)2009 Assistant professor, The University of Tokyo
2014 Associate professor, The University of Tokyo

Research Interests
1) Synthetic organic chemistry2) Organometallic chemistryAwards
2015
2014
2013
2012
2009



Thieme Chemistry Journal Award
Banyu Chemist Award
Diploma of Excellency from the Ministry of Education of Romania
Chemistry Innovation GCOE Lectureship
Incentive Award of the Graduate School of Science, The University of Tokyo

Recent Publications
1. "Iron-catalyzed C(sp2)–H Bond Functionalization with Organoboron Compounds", R.
Shang, L. Ilies, S. Asako, and E. Nakamura, J. Am. Chem. Soc. 2014, 136, 14349.
2. "Iron-Catalyzed Directed Alkylation of Aromatic and Olefinic Carboxamides with Primaryand Secondary Alkyl Tosylates, Mesylates, and Halides", L. Ilies, T. Matsubara, S.
Ichikawa, S. Asako, and E. Nakamura, J. Am. Chem. Soc. 2014, 136, 13126.
3. "Synthesis of Anthranilic Acid Derivatives through Iron-Catalyzed Ortho Amination of
Aromatic Carboxamides with N-Chloroamines", T. Matsubara, S. Asako, L. Ilies, and E.
Nakamura, J. Am. Chem. Soc. 2014, 136, 646.
4. "Iron-Catalyzed Ortho Allylation of Aromatic Carboxamides with Allyl Ethers", S. Asako,
L. Ilies, and E. Nakamura, J. Am. Chem. Soc. 2013, 135, 17755.
5. "-Arylation of Carboxamides via Iron-Catalyzed C(sp3)–H Bond Activation", R. Shang, L.
Ilies, A. Matsumoto, and E. Nakamura, J. Am. Chem. Soc. 2013, 135, 6030.

Molecular Activation Directed toward Straightforward Organic Synthesis

Directed C–H Bond Activation
Using Iron Catalysis
Laurean ILIES and Eiichi NAKAMURA
Department of Chemistry, School of Science, The University of Tokyo, Hongo,
Bunkyo-ku, Tokyo 113-0033, Japan
Iron-catalyzed C–H bond activation is of interest because iron is abundant,
inexpensive, and non-toxic, and direct functionalization of simple substrates
streamlines the synthetic strategy. However, the reactivity of catalytic organoiron
species is difficult to control,1 hampering the development of efficient and selective
reactions. This presentation will describe our journey from a scientificallyinteresting, but synthetically insignificant oxidative C–H bond functionalization
catalyzed by low-valent iron species,2 to the development of the reaction of C–H
bonds with electrophiles enabled by a bidentate directing group and a diphosphine
ligand bearing a -conjugated backbone,3 and finally the design of anorganoiron(III) catalyst that could achieve versatility comparable with and evensurpassing precious metal catalysis.4

Figure 1. From low-valent iron to organoiron(III) species for directed C–H bond activation.

References
1) Ilies, L.; Nakamura, E. in The Chemistry of Organoiron Compounds; Eds. Marek, I.;
Rappoport, Z.; John Wiley & Sons, Ltd.: Chichester, UK, 2014.
2) Selected examples: (a) Matsumoto, A.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2011,
133, 6557. (b) Ilies, L.; Asako, S.; Nakamura, E. J. Am. Chem. Soc. 2011, 133, 7672. (c)Shang, R.; Ilies, L.; Matsumoto, A.; Nakamura, E. J. Am. Chem. Soc. 2013, 135, 6030.
3) (a) Asako, S.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2013, 135, 17755. (b) Matsubara,T.; Asako, S.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2014, 136, 646.
4) (a) Shang, R.; Ilies, L.; Asako, S.; Nakamura, E. J. Am. Chem. Soc. 2014, 136, 14349. (b)Ilies, L.; Matsubara, T.; Asako, S.; Ichikawa, S.; Nakamura, E. J. Am. Chem. Soc. 2014,
136, 13126.

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5th CCS-CSJ, Young Chemists Forum

Shang-Dong YANG
State Key Laboratory of Applied Organic Chemistry,
Lanzhou University, 730000, Lanzhou,
P. R. China
Tel & Fax: 0086-(0)931-8912859(o)Email: yangshd@lzu.edu.cn


Educational Background1997 B.Sc., Dept. of Chemistry, Lanzhou University
2006 Ph.D, Lanzhou University (Supervisor: Prof. Yongmin Liang)
2006-2007 Postdoctoral research at Peking University (Supervisor: Zhangjie Shi), China
2007-2009 Postdoctoral research at The University of Chicago (Supervisor: Chuan He),USA

Professional Career2009 Professor, Lanzhou University



Research Interests
1) The Development of New and Efficient Methodologies for C-P Bond Formation
2) Asymmetric C-H Functionalization

Awards
2011 "New Century Excellent Talents in University Award" from Chinese Ministry of
Education2015 Thieme Chemistry Journal Award

Recent Publications
1. Enantioselective Synthesis of Arylglycine Derivatives by Direct C–H Oxidative Cross-coupling, Wei,
X.-H.; Wang, G.-W. And Yang, S.-D.*, Chem. Commun., 2015, 51, 832—835.
2. Regio- and Stereoselective Allylic C−H Arylation with Electron-Deficient Arenes by 1,1 ′-Bi-2-naphthol−Palladium Cooperation, Wang, G.-W.; Zhou, A.-X.; Li, S.-X. And Yang, S.-D.*, Org.
Lett. 2014, 16, 3118-3121.
3. Palladium-catalyzed P(O)R2 directed C–H arylation to synthesize electron-rich polyaromatic
monophosphorus ligands, Hu, R.-B.; Zhang, H.; Zhang, X.-Y. And Yang, S.-D.*, Chemm. Commun.
2014, 50, 2193-2195.
4. A unique Copper-catalyzed Cross-coupling Reaction by Hydrogen (H2) Removal for the
Stereoselective Synthesis of 3-phosphoindoles, Zhou, A.-X.; Mao, L.-L.; Wang, G.-W.; And Yang,
S.-D.*, Chemm. Commun. 2014, 50, 8529-8532.
5. Direct Annulations toward Phosphorylated Oxindoles: Silver-Catalyzed Carbon-Phosphorus
Functionalization of Alkenes, Li, Y.-M.; Sun, M.; Wang, H.-L.; Tian, Q.-P. And Yang, S.-D.*, Angew.
Chem. Int. Ed., 2013, 52, 3972–3976.
6. Pd(II)-Catalyzed Ph2(O)P-Directed C-H Olefination toward Phosphine-alkene Ligands, Wang, H.-L.;
Hu, R.-B.; Zhang, H.; Zhou, A.-X. And Yang, S.-D.*, Org. Lett. 2013, 15, 5302-5305.
7. Nickel-Catalyzed C-P Cross-Coupling via C-CN Bond Cleavage, Sun, M.; Zhang, H.-Y.; Han, Q.;
Yang, K. And Yang, S.-D.*, Chem. Eur. J. 2011, 17. 9566–3976.
8. Copper-Catalyzed C-P Coupling via Decarboxylation, Hu, J.; Zhao, N.; Yang, B.; Wang, G.; Guo,
L.-N.; Liang, Y.-M. And Yang, S.-D.*, Chem. Eur. J. 2011, 17. 5516–5521.

Molecular Activation Directed toward Straightforward Organic Synthesis

Phosphine-Participated C-H Transformation
An-Xi ZHOU, Bin YANG, Liu-Liang MAO, and Shang-Dong YANG*
State Key Laboratory of Applied Organic Chemistry, Lanzhou University

Lanzhou 730000, P. R. China
Aromatic organophosphorus compounds play very important roles and are
ubiquitous. They can be found in a wide range of nucleotides, pharmaceuticals,
and phosphine-containing ligands. Therefore, the development of a more concise
and efficient method for the C-P bond formation is highly desirable and presents
a considerable challenge to research. Recently, transition-metal-catalyzed direct
C–H activation and functionalization have become powerful tools in organic
synthesis by virtue of the step economy, lower-cost, and decreased waste
production. With recent efforts, our group explored and developed some new
methodologies of C-P bond construction by transition metal-catalyzed
dehydrogenative cross-coupling reactions (Figure 1). Moreover, by using thediphenylphosphine oxide (P(O)Ph2) as directing group, our group also developed
a series of the Pd(II)-catalyzed P(O)Ph2-directed C-H functionalizations tosynthesis different phosphine ligands (Figure 2).

References:
1. Hu, R.-B.; Zhang, H.; Zhang, X.-Y. And Yang, S.-D.*, Chemm. Commun. 2014, 50,
2193-2195.
2. Zhou, A.-X.; Mao, L.-L.; Wang, G.-W.; And Yang, S.-D.*, Chemm. Commun. 2014, 50,
8529-8532.
3. Li, Y.-M.; Sun, M.; Wang, H.-L.; Tian, Q.-P. And Yang, S.-D.*, Angew. Chem. Int. Ed.,2013, 52, 3972–3976.
4. Wang, H.-L.; Hu, R.-B.; Zhang, H.; Zhou, A.-X. And Yang, S.-D.*, Org. Lett. 2013, 15,5302-5305.

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5th CCS-CSJ, Young Chemists Forum

Junichiro YAMAGUCHI
Associate Professor
Graduate School of Science, Nagoya University
Furo-cho, Chikusa, Nagoya 464-8602, Japan
Phone: +81-52-789-5873
E-mail: junichiro@chem.nagoya-u.ac.jp

Educational Background2002 B.Sc. Tokyo University of Science, Japan (supervisor: Prof. Yujiro Hayashi)
2004 M.Sc. Graduate School of Engineering, Tokyo University of Science, Japan (supervisor:
Prof. Yujiro Hayashi)
2006 Exchange Student, The Scripps Research Institute, USA (Prof. K. C. Nicolaou)2007 Doctor of Engineering, Graduate School of Engineering, Tokyo University of Science,
Japan (supervisor: Prof. Yujiro Hayashi)Professional Career2007 Postdoctoral Researcher, The Scripps Research Institute, USA (with Professor. Phil S.
Baran)
2008 Assistant Professor, Graduate School of Science, Nagoya University, Japan (withProfessor Kenichiro Itami)
2012 Associate Professor, Graduate School of Science, Nagoya University, Japan

Research Interests
1)
2)



Organic synthesis
Synthesis of natural productsAwards2009 Teijin Pharma Award in Synthetic Organic Chemistry, Japan
2011 Young Scientist’s Research Award in Natural Product Chemistry, Japan
2012 The Chemical Society of Japan Lecture Award for Young Chemists
2013 Japan Union of Chemical Science and Technology Chemistry Communication Award
2013 The Chemical Society of Japan Award for Distinguished Young Chemists
2014 Banyu Chemist Award
2014 Thieme Chemistry Journal Award
2014 Asian Core Lectureship Award, China and Thailand

Recent Publications
1. "Synthesis and characterization of hexaarylbenzenes with five or six different substituents enabled byprogrammed synthesis ", Suzuki, S.; Segawa, Y.; Itami, K. Yamaguchi, J. Nature Chem. 2015. 7, 277.
2. "Concise Syntheses of Dictyodendrins A and F by a Sequential C−H Functionalization Strategy ",Yamaguchi, A.; Chepiga, K.; Yamaguchi, J.; Itami, K.; Davies, H. J. Am. Chem. Soc. 2015, 137, 644.
3. “Stereodivergent Synthesis of Arylcyclopropylamines by Sequential C–H Borylation andSuzuki–Miyaura Coupling” Miyamura, S.; Araki, M.; Suzuki, T.; Yamaguchi, J.; Itami, K. Angew.
Chem., Int. Ed. 2015, 54, 846.
4. “β-Selective C–H Arylation of Pyrroles Leading to Concise Syntheses of Lamellarins C and I“ Ueda,
K.; Amaike, K.; Maceiczyk, R. M; Itami, K.; Yamaguchi, J. J. Am. Chem. Soc. 2014, 136, 13226.

Molecular Activation Directed toward Straightforward Organic Synthesis

A C–H Arylation/Ring Transformation Approach:
Synthesis of Polyarylated Arenes
and Natural Products
Junichiro YAMAGUCHI
Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho,
Chikusa, Nagoya 464-8602, Japan
Polyarylated arenes are privileged structures with many interesting functions andfascinating optoelectronic or biological properties, and therefore, the construction of thesescaffolds has been a topic of great importance in chemistry. Recently, the C–H arylation
method of arenes has garnered much attention from the synthetic chemistry community as anext-generation coupling method to construct such motifs. The development of C–Harylation of five-membered heteroarenes with controlled regioselectivity has been wellestablished. However, the C–H arylation of six-membered aromatics such as benzenes andpyridines has considerable room for further investigations in terms of overcoming
challenges in reactivity and regioselectivity. To address these issues and to synthesize
polyarylated arenes, the regioselective C–H arylation of five-membered heteroarenes,
followed by a ring transformation approach, has been developed.
To this end, the synthesis and characterization of hexaarylbenzenes with five or six
different aryl groups was achieved by first a C–H arylation of thiophenes, followed by
thiophene oxidation, then a [4+2] cycloaddition of the resulting tetraarylthiophene S-oxide.
Furthermore, a formal synthesis of GE2270A, a thiopeptide antibiotic, has beenaccomplished by using this approach (Figure 1).

Figure 1. Synthetic Targets with Multiply Arylated Six-membered Arenes as the Core Structure.

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5th CCS-CSJ, Young Chemists Forum

Guangxin LIANG
Professor of Chemistry
State Key Laboratory of Elemento-organic Chemistry, Nankai
University
Address: 94 Weijin Road, Tianjin, China
Tel & Fax: (+86)-22-2350-0867
E-mail: lianggx@nankai.edu.cn


Educational Background1997 B.Sc., Nankai University (supervisor: Prof. Manxue Yuan)
2002 M.Sc., Department of Chemistry, The Ohio-State University (supervisor: Prof. Todd Lowary)
2007 Ph.D., Department of Chemistry, UC, Berkeley (supervisor: Prof. Dirk Trauner)Professional Career2007 Senior Research Scientist, Global Pharmaceutical R&D Division, Abbott Laboratories
2009 Professor, Nankai University



Research Interests
1)
2)



Total synthesis of structurally intriguing natural products of biological and medicinal
interests.
Large scale synthesis and process development of important active pharmaceuticalingredients.

Awards2004 Roche Graduate Fellowship, USA
2005 Bristol-Myers Squibb Graduate Fellowship, USA
2006 Thieme SYNStar Award, USA
2008 Excellent Performance Award, Abbott Labortories, USA
2008 Robert G. Stern Award, Abbott Laboratories, USA
2012 ACP Lectureship Awards, Singapore
2013 Young Investigator of the New Century, Ministry of Education, China

Recent Publications
1. "Total Synthesis of (–)-Isatisine A", Zhang, X.; Mu, T.; Zhan, F.; Ma, L.; Liang, G.* Angew. Chem.
Int. Ed. 2011, 50, 6164.
2. "Rapid Construction of the ABC Ring System in the Daphniphyllum Alkaloid Daphniyunnine C",
Yao, Y.; Liang, G.* Org. Lett. 2012, 14, 5499.
3. "Formation of Enehydrazine Intermediates through Coupling of Phenylhydrazines with Vinyl
Halides: Entry into the Fischer Indole Synthesis", Zhan, F.; Liang, G.* Angew. Chem. Int. Ed. 2013,
52, 1266.
4. "Total Syntheses of Echinopines", Xu, W.; Wu, S.; Zhou, L.; Liang, G.* Org. Lett. 2013, 15, 1978.
5. "Total Synthesis of Mersicarpine through a Cationic Cyclization Approach", Lv, Z.; Li, Z.; Liang,
G.* Org. Lett. 2014, 16, 1653.
6. "Total Syntheses of (±)-Omphadiol and (±)-Pyxidatol C through a Cis-Fused 5,7-Carbocyclic
Common Intermediate", Zhou, L.; Yao, Y.; Xu, W.; Liang, G.* J. Org. Chem. 2014, 79, 5345.
7. "Selective Syntheses of Leuconolam, Leuconoxine, and Mersicarpine Alkaloids from a Common
Intermediate through Regiocontrolled Cyclizations by Staudinger Reactions ", Li, Z.; Geng, Q.; Lv,
Z.; Pritchett, B. P.; Baba, K.; Numajiri, Y.; Stoltz, B. M.*; Liang, G.* Org. Chem. Front. 2014, In
Print

Molecular Activation Directed toward Straightforward Organic Synthesis

Act like Molecule Transformers ─
Rapid Creation of Molecular Complexity throughStrategic Bond Disconnections
Guangxin LIANG,* Wenbo XU, Yaomin YAO, Fuxu ZHAN, Zining LI, and Zhe LV
State Key Laboratory of Elemento-organic Chemistry, Nankai University,
Tianjin, P. R. China
Creation of new substances is the central value of chemistry. To understand the new
substances and to further use it as a probe to explore the world require synthetic science,
the major platform for chemists to perform such creation, to be able to synthesize in an
efficient way. Creation of molecular complexities rapidly from relative simple ones is
one of the solutions for efficient synthesis. We believe strategic bond disconnections
play a vital role in synthetic design so that to develop efficient synthesis. Synthetic
examples will be discussed to demonstrate how we rapidly created molecularcomplexity based on this guideline.

Figure: Targets Synthesized through Rapid Creation of Molecular Complexities.

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5th CCS-CSJ,
Young Chemists Forum

20

Mamoru TOBISU
Associate Professor of ChemistryCenter for Atomic and Molecular Technologies, Graduate School ofEngineering, Osaka University
Address: Yamadaoka 2-1, Suita, Osaka 565-0871
Tel: (+81)-6-6879-7395
E-mail: tobisu@chem.eng.osaka-u.ac.jp
Educational Background1996 B.Sc., Osaka University (supervisor: Prof. Shinji Murai)
1998 M.Sc., Graduate School of Engineering, Osaka University(supervisor: Prof. Shinji Murai)
2001 Doctor of Engineering, Graduate School of Engineering,Osaka University (supervisor: Prof. Shinji Murai)

Professional Career
2001 Takeda Pharmaceutical Company
2005 Assistant professor, Osaka University
2011 Associate professor, Osaka University



Research Interests
1) Synthetic Organic Chemistry2) Organometallic ChemistryAwards2009 The Chemical Society of Japan Award For Young Chemists
2012 The Young Scientists' Prize from the Ministry of Education,
Culture, Sports, Science and Technology, Japan
2012 Merck-Banyu Lectureship Award

Recent Publications
1. "Rhodium-Catalyzed Borylation of Aryl 2-Pyridyl Ethers through Cleavage of the CarbonOxygen Bond: Borylative Removal of the Directing Group", H. Kinuta, M. Tobisu,* and N.
Chatani* J. Am. Cem. Soc. in press
2. "Nickel-Catalyzed Alkynylation of Anisoles via C-O Bond Cleavage", M. Tobisu,* T. Takahira,A. Ohtsuki, and N. Chatani* Org. Lett. in press
3. "Rhodium-Catalyzed Borylation of Aryl and Alkenyl Pivalates through Cleavage ofCarbon‒Oxygen Bonds", H. Kinuta, J. Hasegawa, M. Tobisu,* and N. Chatani* Chem. Lett. inpress
4. "Palladium-Catalyzed Synthesis of Six-Membered Benzofuzed Phosphacycles via CarbonPhosphorus Bond Cleavage", K. Baba, M. Tobisu,* and N. Chatani* Org. Lett. 2015, 17, 70.
5. "1,3-Dicyclohexylimidazol-2-ylidene as a Superior Ligand for the Nickel-Catalyzed CrossCouplings of Aryl and Benzyl Methyl Ethers with Organoboron Reagents", M. Tobisu,* A.
Yasutome, H. Kinuta, K. Nakamura, and N. Chatani*, Org. Lett. 2014, 16, 5572.
6. "Nickel-Catalyzed Reductive and Borylative Cleavage of Aromatic Carbon-Nitrogen Bonds in NAryl Amides and Carbamates", M. Tobisu,* K. Nakamura, and N. Chatani* J. Am. Chem. Soc.
2014, 136, 5587.

Molecular Activation Directed toward Straightforward Organic Synthesis

Cross-Coupling Reactions via the Activationof Inert Carbon-Oxygen Bonds
Mamoru TOBISU
Center for Atomic and Molecular Technologies, Osaka University,
Suita, Osaka 565-0871, Japan

Arene synthesis has been revolutionized by the invention of catalytic crosscoupling reactions, wherein aryl halides are coupled with organometallic and organic
nucleophiles. Although the replacement of aryl halides with phenol derivatives as
substrates would lead to more economical and ecological methods, success has been
primarily limited to the use of activated phenol derivatives such as triflates. Aryl ethers
arguably represents one of the most ideal substrates in terms of their availability, cost,safety and atom efficiency. However, among the various phenol derivatives, the robust
nature of C(aryl)-O bonds in aryl ethers makes it extremely difficult to use in catalytic
reactions.
Since the seminal work by Wenkert in 1979 on the nickel-catalyzed cross-couplingof aryl ethers with Grignard reagents, progress in this field has been relatively slow.
One reason for this is that the accumulated knowledge regarding palladium-catalyzed
cross-couplings was not readily translated to nickel catalysis, in particular, in cases ofaryl ether substrates. In this symposium, we report on advances that have been made in
the cross-coupling of aryl ethers over the last decade, with particular emphasis on
contributions from our laboratory.

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Molecular Activation Directed toward Straightforward Organic Synthesis

Yoshiaki NAKAO
Professor of Chemistry
Department of Material Chemistry, Graduate School of Engineering,
Kyoto University
Address: Nishikyo-ku, Kyoto 615-8510
Tel: (+81)-75-383-2443
Fax: (+81)-75-383-2445
E-mail: nakao.yoshiaki.8n@kyoto-u.ac.jp
Educational Background1998 B.Sc., Kyoto University (supervisor: Prof. Tamejiro Hiyama)
1998 M.Sc., Graduate School of Engineering, Kyoto University (supervisor: Prof.
Tamejiro Hiyama)
2005 Doctor of Engineering, Graduate School of Engineering, Kyoto University(supervisor: Prof. Tamejiro Hiyama)Professional Career
2002 Assistant professor, Kyoto University
2010 Senior lecturer, Kyoto University
2011 JST-PRESTO Researcher
2012 Associate professor, Kyoto University
2014 Professor, Kyoto University
2014 JST-CREST Researcher



Research Interests
1) Organic synthesis
2) Organometallic chemistryAwards2009 Mitsui Chemicals Catalysis Science Award of Encouragement
2009 The Society of Silicon Chemistry Award of Encouragement
2010 Thieme Journal Award
2010 Merck–Banyu Lectureship Award
2011 The Chemical Society of Japan Award for Young Chemists
2011 The Young Scientist’s Prize from the Ministry of Education, Culture, Sports, Scienceand Technology
2015 Tetrahedron Young Investigator Award

Recent Publications
1. "Intramolecular Oxycyanation of Alkenes by Cooperative Pd/BPh3 Catalysis", D. C. Koester, M.
Kobayashi, D. B. Werz, and Y. Nakao. J. Am. Chem. Soc. 2012, 134, 6544.
2. "Intramolecular Aminocyanation of Alkenes by Cooperative Palladium/Boron Catalysis", Y.
Miyazaki, N. Ohta, K. Semba, and Y. Nakao. J. Am. Chem. Soc. 2014, 136, 3732.
3. "Arylboration of Alkenes by Cooperative Palladium/Copper Catalysis", K. Semba and Y. Nakao. J.
Am. Chem. Soc. 2014, 136, 3732.